The present invention relates to the field of fiber-reactive dyes.
Black-dyeing mixtures of fiber-reactive dyes are known from U.S. Pat. Nos. 5,445,654 and 5,611,821 as well as from Korean Patent Application Publication No. 94-2560. Deep black dye mixtures are known, for example, from Japanese Patent Application Publication Sho-58-160 362 which are based on a navy-blue disazo dye and an orange monoazo dye. However these dye mixtures have some deficiencies.
With the present invention, deep black-dyeing dye mixtures of improved properties, for example wash fastnesses have unexpectedly been found, comprising a disazo dye conforming to the general formula (1), 
and one or more disazo dyes conforming to the general formula (2), 
wherein:
M is hydrogen or an alkali metal, such as lithium, sodium and potassium;
n is in each case independently 0 or 1;
R1 is hydrogen, methyl, methoxy, sulfo, cyano, or chloro preferably hydrogen;
R2, R3, R4, R5, R6 have one of the meanings of R1;
R11 is hydrogen or alkyl or phenyl, which may be mono- or di-substituted by an alkyl, alkoxy, ester, ureido, carboxamido, hydroxy, chloro, cyano or sulfo group;
L1 is a fiber-reactive group of the formulae (5a-d): 
wherein:
R12 has one of the meanings of R11;
Y is in each instance, independently of one another, vinyl or is ethyl which is substituted in the xcex2-position by a substituent which can be eliminated by the action of an alkali, forming the vinyl group, such as chlorine, thiosulfato, sulfato, alkanoyloxy of 2 to 5 carbon atoms, such as acetyloxy, phosphato, sulfobenzoyloxy and p-toluylsulfonyloxy, and is preferably vinyl, xcex2-chloroethyl, xcex2-thiosulfatoethyl or xcex2-sulfatoethyl and is in particular preferably vinyl or xcex2-sulfatoethyl;
*xe2x80x94denotes the bond to the aromatic ring;
X denotes chloro or fluoro and
Z has one of the meanings of X or is hydrogen or cyano;
Q is chloro, fluoro, cyanamido, hydroxy, alkoxy of 1 to 4 carbon atoms, pyridino, carboxypyridino, carbamoylpyridino a group of the general formula W or is a group of the general formulae (6a) or (6b), 
in which
R13 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, sulfoalkyl of 1 to 4 carbon atoms, phenyl unsubstituted or substituted by 1 to 2 substituents selected from the group of substituents consisting of chlorine, bromine, methyl, ethyl, methoxy, sulfo, acetamido, ureido and carboxy;
R14 has one of the meanings given for R13;
R15 has one of the meanings given for R13, or
R13 and R14 form a cyclic ringsystem of the general formulae (6c) or (6d) 
wherein
Rxc2x0 is a heterogroup such as O, S, SO2 or NR12 or is a methylene group;
G is arylene, C1-C6-alkylene or alkylene-arylene, each unsubstituted or substituted, wherein the alkylene moieties being preferably those of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms, in particular of 1 to 3 carbon atoms, such as methylene, ethylene and n-propylene, or being preferably of 2 to 6 carbon atoms, if interrupted by a hetero group, such as O, S, NH, SO2, CO, COxe2x80x94NH, NHxe2x80x94CO, arylene being phenylene or naphthylene, the substituents of phenylene being preferably 1 or 2 substituents selected from the group consisting of alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, carboxy, sulfo and chlorine, in particular thereof methyl, ethyl, methoxy and ethoxy, and the substituents of naphthylene being preferably 1 or 2 sulfo groups;
L2, L3 have one of the meanings of L1;
W is a phenyl group of the general formula (3) or naphtyl group of the general formula (4) 
in which
M is defined as above;
* denotes the bond to the diazo group;
R7, R8, R9, R10 have one of the meanings of R1;
n is in each case independently 0 or 1 and
L4, L5 have one of the meanings of L1.
Preference is given to dye mixtures comprising an amount of from 40 to 95% by weight of one or more disazo dyes of the general formula (1) and from 1 to 60% by weight of one or more disazo dyes of the general formula (2) based on the dye mixture.
Special preference is given to dye mixtures comprising an amount of from 60 to 80% by weight of one or more disazo dyes of the general formula (1) and from 20 to 40% by weight of one or more disazo dyes of the general formula (2) based on the dye mixture.
The groups xe2x80x9csulfoxe2x80x9d, xe2x80x9cthiosulfatoxe2x80x9d, xe2x80x9ccarboxyxe2x80x9d, xe2x80x9cphosphatxe2x80x9d and xe2x80x9csulfatoxe2x80x9d include both the acid form and the salt form of these groups. Accordingly, sulfo groups are groups of the formula xe2x80x94SO3M, thiosulfato groups are groups of the formula xe2x80x94Sxe2x80x94SO3M, carboxy groups are groups of the formula xe2x80x94COOM, phosphat groups are groups of the formula xe2x80x94OPO3M2 and sulfato groups are groups of the formula xe2x80x94OSO3M, in which M is defined as above.
The dye mixtures according to the present invention may also comprise one or more monoazo dye of the general formulae (7) or (8) in up to 5% by weight: 
wherein M, R3, R4, and L2 are as defined above.
In addition the dye mixtures may contain up to about 15% by weight of a commercially available red reactive dyestuff. These shading components are well known in the literature and can be synthesized by the standard methods. They are generally added as shading components. Examples of these are in particular dyes of the formulas (I), (II) or (III) 
wherein
X, M, Q, R3, R4, L2, n are as described above.
The dyes of the general formulae (1), (2), (7), (8), (I), (II), in particular if those corresponding to the same general formula, have the same chromophore, can have, within the meaning of Y, structurally different fiber-reactive groups xe2x80x94SO2xe2x80x94Y. In particular, the dye mixture can contain dyes of the same chromophore conforming to the formula (1) and dyes of the same chromophore conforming to formula (2) and optionally likewise of the general formula (7) and (8) in which the fiber-reactive groups xe2x80x94SO2xe2x80x94Y are partly vinylsulfonyl groups and partly groups in which Y is a xcex2-ethyl substituted group as defined above, such as xcex2-chloroethylsulfonyl, xcex2-thiosulfatoethylsulfonyl or, preferably, xcex2-sulfatoethylsulfonyl groups. If the dye mixtures contain the respective dye components in the form of a vinylsulfonyl dye, the proportion of the respective vinylsulfonyl dye to the respective dye with Y being a xcex2-ethyl substituted group as defined above, such as a xcex2-chloro- or xcex2-thiosulfato- or xcex2-sulfatoethyl-sulfonyl dye, will be up to about 30 mol-%, based on the respective dye chromophore. Preference is here given to the dye mixtures in which the proportion of vinylsulfonyl dye to said xcex2-ethyl substituted dye, such as xcex2-sulfatoethylsulfonyl dye is in terms of the molar ratio between 5:95 and 30:70.
The dye mixtures of the invention can be present as a preparation in solid or liquid (dissolved) form. In solid form they generally contain the electrolyte salts customary in the case of water-soluble and in particular fiber-reactive dyes, such as sodium chloride, potassium chloride and sodium sulfate, and also the assistants customary in commercial dyes, such as buffer substances capable of establishing a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium citrate, sodium dihydrogenphosphate and disodium hydrogenphosphate, small amounts of siccatives or, if they are present in liquid, aqueous solution (including the presence of thickeners of the type customary in print pastes), substances which ensure the permanence of these preparations, for example mold preventatives.
If the dye mixtures take the form of dye powders, they contain, as a rule, 10 to 60% by weight, based on the dye powder or preparation, of a strength-standardizing colorless diluent electrolyte salt, such as those mentioned above. These dye powders may in addition contain the above mentioned buffer substances in a total amount of up to 10%, based on the dye powder. If the dye mixtures of the invention are present in aqueous solution, the total dye content of these aqueous solutions is up to about 75% by weight, the electrolyte salt content of these aqueous solutions preferably being below 10% by weight, based on the aqueous solutions (liquid preparations) can in general contain the above mentioned buffer substances in an amount of up to 10% by weight, preferably up to 5% by weight.
The disazo dyes of the general formula 2 are new if the amide group is in the 6 position relative to the hydroxyl group and the xe2x80x94SO3M group is in the 5 position relative to the hydroxyl group, as given in general formula (2-1), 
or if the amide group is in 7 position and the xe2x80x94SO3M group is in position 6 relative to the hydroxyl group, as given in general formula (2-2) 
wherein
M is hydrogen or an alkali metal, such as lithium, sodium and potassium;
R5, R6 is hydrogen, methyl, methoxy, sulfo, cyano, or chloro preferably hydrogen;
R11 is hydrogen or alkyl or phenyl, which may be mono- or di-substituted by an alkyl, alkoxy, ester, ureido, carboxamido, hydroxy, chloro, cyano or sulfo group;
L3 is a fiber-reactive group of the formulae (5a-d): 
wherein:
R12 has one of the meanings of R11;
Y is in each instance, independently of one another, vinyl or is ethyl which is substituted in the xcex2-position by a substituent which can be eliminated by the action of an alkali, forming the vinyl group, such as chlorine, thiosulfato, sulfato, alkanoyloxy of 2 to 5 carbon atoms, such as acetyloxy, phosphat, sulfobenzoyloxy and p-toluylsulfonyloxy, and is preferably vinyl, xcex2-chloroethyl, xcex2-thiosulfatoethyl or xcex2-sulfatoethyl and is in particular preferably vinyl or xcex2-sulfatoethyl;
*xe2x80x94denotes the bond to the aromatic ring;
X denotes chloro or fluoro and
Z has one of the meanings of X or is hydrogen or cyano;
Q is chloro, fluoro, cyanamide, hydroxy, alkoxy of 1 to 4 carbon atoms, pyridino, carboxypyridino, carbamoylpyridino a group of the general formula W or is a group of the general formulae (6a) or (6b), 
in which
R13 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, sulfoalkyl of 1 to 4 carbon atoms, phenyl unsubstituted or substituted by 1 to 2 substituents selected from the group of substituents consisting of chlorine, bromine, methyl, ethyl, methoxy, sulfo, acetamido, ureido and carboxy;
R14 has one of the meanings given for R13;
R15 has one of the meanings given for R13, or
R13 and R14 form a cyclic ring system of the general formulae (6c) or (6d) 
Rxc2x0 is a hetero group such as O, S, SO2 or NR12 or is a methylene group;
G is arylene, C1-C6-alkylene or alkylene-arylene, each unsubstituted or substituted, wherein the alkylene moieties being preferably those of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms, in particular of 1 to 3 carbon atoms, such as methylene, ethylene and n-propylene, or being preferably of 2 to 6 carbon atoms, if interrupted by a hetero group, such as O, S, NH, SO2, CO, COxe2x80x94NH, NHxe2x80x94CO, arylene being phenylene or naphthylene, the substituents of phenylene being preferably 1 or 2 substituents selected from the group consisting of alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, carboxy, sulfo and chlorine, in particular thereof methyl, ethyl, methoxy and ethoxy, and the substituents of naphthylene being preferably 1 or 2 sulfo groups;
W1 is a phenyl group of the general formula (3) or naphtyl group of the general formula (4) 
in which
M is defined as above;
* denotes the bond to the diazo group;
R7, R8, R9, R10 are hydrogen, methyl, methoxy, sulfo, cyano, or chloro;
n is in each case independently 0 or 1 and
L4, L5 have one of the meanings of L3.
W2 is a phenyl group of the general formula (3xe2x80x2) or naphtyl group of the general formula (4xe2x80x2) 
in which
M is defined as above;
* denotes the bond to the diazo group;
R7xe2x80x2, R8xe2x80x2, are hydrogen, methoxy, methyl
R9xe2x80x2, R10xe2x80x2 is hydrogen methyl, methoxy, sulfo, cyano;
n is in each case independently 0 or 1 and
L4, L5 have one of the meanings of L3.
and are thus part of the invention.
The dye mixtures of the invention can be obtained in a conventional manner, for instance by mechanically mixing the individual dyes in the required proportions or by synthesis by means of the customary diazotization and coupling reactions using appropriate mixtures of the diazo and coupling components in a manner familiar to those skilled in the art and the necessary proportions. One option is for example to prepare aqueous suspensions of the coupling components 1-amino-8-naphthol-3,6-disulfonic acid and for example 1-hydroxy-3,5-disulfo-6-N-(1 xe2x80x2, 3xe2x80x2-diketobutyl)-naphtylamine, and as diazo components, aniline compounds of the formula (9). 
Thus the dye mixture can be produced by diazotizing 4-(xcex2-sulfatoethylsulfonyl)-aniline (9) in a conventional manner in a strongly acid medium and then carrying out the coupling reaction of the 1-amino-8-napthol-3,6-disulfonic acid with the diazo component at a pH below 1.5 to form the compound (7). The second coupling reaction with the monoazo dye (7) giving the disazo dyes conforming to the formula (1) is carried out at a pH between 3 and 6.5. Then, by addition of the aqueous solution of the acetoacetylated napthylamine the coupling reaction to form the dye conforming to the general formula (2) is carried out at a pH between 1 and 6.5. The inventive dyestuff mixture can be isolated from the solution in the conventional manner, for example by salting out with an electrolyte salt, such as sodium chloride or potassium chloride, or by spray-drying.
The acetoacetylated coupling agents employed are readily obtained by reaction of the appropiately substituted naphtylamines with an excess of 5-200% of diketene in aqueous solution between 0-60xc2x0 C., preferably between 30-50xc2x0 C. and at a pH between 3 and 11 preferably at pH 4 to 8. The resulting acetoacetylated products can subsequently be used directly for the diazo coupling reaction or can be isolated by conventional salting out or spray drying. If the reaction solutions are used directly, excess acylating agent can be removed by heating to approximately 80xc2x0 C.
Dyes of the general formula (2) wherein the azo moieties are of a different structure are prepared preferably by diazotizing the aromatic amine having the structure
Wxe2x80x94NH2 
wherein W is as defined above and coupling the resulting diazo-compound to the naphtylamine of the formula (10) 
wherein M, R11 and n are defined as above and then acetoacetylating the intermediate as described above with subsequent coupling with a second diazo at the 1,3-diketo moiety.
Dye mixtures in which the dye chromophores contain for example not only a xcex2-chloroethylsulfonyl or xcex2-thiosulfatoethylsulfonyl or xcex2-sulfatoethylsulfonyl group but also proportions with vinylsulfonyl groups cannot only be prepared by the above mentioned method using appropriate vinylsulfonyl starting anilines, but also by reacting the dye mixture in which Y is a xcex2-chloroethyl, xcex2-thiosulfatoethyl, or xcex2-sulfatoethyl radical with an amount of alkali required for only part of these groups and converting part said xcex2-substituted ethylsulfonyl groups into vinylsulfonyl groups. This reaction is carried out by generally known methods of converting xcex2-substituted ethylsulfonyl groups into the vinylsulfonyl group.
The dye mixtures of the instant invention are well suitable for dyeing (which includes printing) hydroxyl- and/or carboxamido-containing fiber materials by the application and fixing methods numerously described in the art for fiber-reactive dyes, in deep black shades with good color build-up and good wash-off in respect of unfixed dye portions. Moreover, the dyeings obtained show improved wash-fastness.
The present invention therefore also provides for use of the inventive dye mixtures for dyeing (including printing) hydroxyl- and/or carboxamido-containing fiber materials and processes for dyeing such fiber materials and processes for dyeing such materials using a dye mixture according to the invention by applying the dye mixture to the substrate in dissolved form and fixing the dyes on the fiber by the action of an alkali or by heating or both.
Hydroxyl-containing materials are natural or synthetic hydroxyl-containing materials, for example cellulose fiber materials, including in the form of paper, or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton but also other natural vegetable fibers, such as linen, hemp, jute and ramie fibers; regenerated cellulose fibers are for example staple viscose and filament viscose.
Carboxamido-containing materials are for example synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-11, and nylon-4.
Application of the dye mixtures of the invention is by generally known processes for dyeing and printing fiber materials by the known application techniques for fiber-reactive dyes. Since the dyes of the dye mixtures according to the invention are highly compatible with one another, the dye mixtures of the invention are also advantageously useful in exhaust dyeing processes. Applied in this way for example to cellulose fibers from a long liquor ratio at temperatures between 40 and 105xc2x0 C., optionally at temperatures up to 130xc2x0 C., under superatmospheric pressure, and optionally in the presence of customary dyeing assistants with the use of acid-binding agents and optionally neutral salts, such as sodium chloride or sodium sulfate, they produce dyeings in very good color yields with excellent color build-up and consistent shade. One possible procedure is to introduce the material into the warm bath, gradually heat the bath to the desired dyeing temperature, and complete the dyeing process at that temperature. The neutral salts which speed up the exhaustion of the dyes can also if desired not be added to the bath until the actual dyeing temperature has been reached.
Similarly, the conventional printing processes for cellulose fibers, which can either be carried out in single-phase, for example by printing with a print paste containing sodium bicarbonate or some other acid-binding agent and the colorant, and subsequent steaming at from 100 to 103xc2x0 C., or in two phases, for example by printing with a neutral or weakly acid print paste containing the colorant and subsequent fixation either by passing the printed material through a hot electrolyte-containing alkaline bath or by overpadding with an alkaline electrolyte-containing padding liquor and subsequent batching of this treated material or subsequent steaming or subsequent treatment with dry heat, produce strong prints with well defined contours and a clear white ground. Changing fixing conditions has only little effect on the outcome of the prints. Not only in dyeing but also in printing the degrees of fixation obtained with dye mixtures of the invention are very high. The hot air used in dry heat fixing by the customary thermofix processes has a temperature of from 120 to 200xc2x0 C. In addition to the customary steam at from 101 to 103xc2x0 C., it is also possible to use superheated steam and high pressure steam at up to 160xc2x0 C.
Acid-binding agents responsible for fixing the dyes to cellulose fibers are for example water-soluble basic salts of alkali metals and of alkaline earth metals of inorganic or organic acids, and compounds which release alkali when hot. Of particular suitability are the alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids, the preferred alkali metal compounds being the sodium and potassium compounds. These acid-binding agents are for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogenphosphate and disodium hydrogenphosphate.
Treating the dyes of the dye mixtures according to the invention with the acid-binding agents with or without heating bonds the dyes chemically to the cellulose fiber; especially the dyeings on cellulose, after they have been given the usual aftertreatment of rinsing to remove unfixed dye portions, show excellent wet fastness properties, in particular since the unfixed dye portions are readily washed off because of their good cold water solubility.
The dyeings of polyurethane and polyamide fibers are customarily carried out from an acid medium. The dyebath may contain for example acetic acid and/or ammonium sulfate and/or acetic acid and ammonium acetate or sodium acetate to bring it to the desired pH. To obtain a dyeing of acceptable levelness it is advisable to add customary leveling assistants, for example based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or based on a reaction product of for example stearylamine with ethylene oxide. In general the material to be dyed is introduced into the bath at a temperature of about 40xc2x0 C. and agitated therein for some time, the dyebath is then adjusted to the desired weakly acid, preferably weakly acetic acid, pH, and the actual dyeing is carried out at temperature between 60 and 98xc2x0 C.
However, the dyeings can also be carried out at the boil or at temperatures up to 120xc2x0 C. (under superatmospheric pressure).
The examples which follow illustrate the invention. Parts and percentages are by weight, unless otherwise stated. The parts by weight bear the same relation to parts by volume as the kilogram to the liter.